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Physical Pharmacy
Colligative Properties of
Solution
21-05-2017

(a) Solutions: Introduction, types, Dr. Muhammad Sarfraz

concentration expressions, ideal and real
solution, colligative properties, their Assistant Professor
mathematical derivations and applications College of Pharmacy
in pharmacy.
Al Ain University Al Ain
 How to study for it
Lecture notes
Textbooks:

Martin’s Physical Pharmacy and Pharmaceutical

Sciences
– Sinko PJ, 6th edition
P 118 – 127
 Objectives
• Define the colligative properties of solutions (lowering of
vapour pressure, elevation of boiling point, depression of
freezing point and osmotic pressure).

• Understand the relationship between solution concentration

and colligative properties.

• Understand the application of colligative properties

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Colligative properties
Depend mainly on the number of particles in a solution but not
upon the size and nature of particle.
Dilute solution having non volatile solutes have following four
colligative properties.

1- Lowering of vapor pressure

2- Elevation in boiling point
3- Depression in freezing Point
4- Osmotic Pressure
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1- Lowering of the vapour pressure

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Vapor Pressure

What is vapor pressure?

The pressure exerted by the vapor of

the liquid at equilibrium state with
pure liquid itself, at a given
temperature , is called the Vapour
pressure of the liquid.
 VP Lowering
When a nonvolatile solute is combined with a volatile solvent, the
vapor pressure of the solvent is deceased, And this decrease in
VP is called lowering of VP.
Explanation:
When a non volatile solute is dissolved in a pure solvent, the
solute molecule adjust themselves b/w the intermolecular
spaces and attraction forces are produced b/w solute and
solvent. Now the solvent molecules cannot easily escape from
the solution and that results in the lowering of VP at constant
temperature.
On the basis of Raoult's law, the vapor pressure of a solution
containing a nonvolatile solute is lowered proportional to the
relative number of solute particles in solution. 13
 Vapor Pressure Lowering
• Vapour pressure
= pressure of a
saturated vapour
above its liquid

• Escaping tendency
= tendency of a
molecule to leave
one phase of a
system
e.g. liquid to vapour

The presence of a non-volatile solute i.e., a solute that does not have a
vapor pressure of its own (fewer solvent particles are at the solution’s
surface, so less solvent evaporates)
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Effect of Solute on Vapour Pressure

• When a non-volatile and non- electrolyte solute is dissolved in a
solvent, the vapor pressure of the resulting solution is lower than
that of the pure solvent.
• The amount of the vapor pressure lowering is proportional to the
amount of solute and not its identity.
• In case, when any non-volatile and electrolyte is dissolved in the
solvent, the lowering in the vapour pressure will be abnormally
high than that of the non- electrolyte. This is because, the
electrolyte dissociate into ions in the solution, so no. of the particle
will increased and as a result, lowering in vapour pressure will also
high.
• NaCl fully ionizes into 2 ions, while the glucose molecules do not
break apart when dissolving
• Each NaCl will have a GREATER effect on vapor pressure
because it dissociates into more particles than glucose
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2- Elevation of Boiling Point

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Boiling point is defined as the temperature at which the vapor
pressure of a liquid equals to the atmospheric pressure.

Greater the vapour pressure of a liquid, lower will be its boiling

point. Similarly, lower the vapour pressure of the liquid, higher
will be its boiling point.

BP Elevation. If any non-volatile and non- electrolyte solute is

dissolved in the solvent, the escaping tendency of the solvent
molecule is reduced and in turn vapour pressure is also reduced
and ultimately its boiling point will be elevated.
Theoretical plot of the normal boiling point for water (solvent)
as a function of molality in solutions containing sucrose (a
nonvolatile solute) in increasing concentrations.

Note that the normal boiling point of water increases as the

concentration of sucrose increases. This phenomenon is
known as boiling point elevation.
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 Graphical Representation of BP Elevation

Addition of the solute to the solvent reduces the vapour pressure and the boiling curve shifts downwards

Ref. Martin’s Physical Pharmacy and Pharmaceutical Sciences, sixth edition p 420 28
Explanation: As the VP curve of solution lies below that of
solvent, so to reach the normal BP, the temperature is
elevated (i.e. Increased) and this increase in temperature of
solution is called elevation in BP and is given by:
T − To = ΔTb
While lowering of VP is
Δp = po – p
The ratio of elevation of BP (ΔTb) to lowering of VP is
constant at 100°C and written as:

ΔTb / Δp = k ΔTb = k Δp---------Eq-1

Moreover the po is constant (Δp = po – p), the BP elevation may
be considered proportional to Δp/po

ΔTb = k Δp/ po ---------Eq-2

According to Roult’s law Δp/ po = X2

ΔTb = k X2 -----------Eq-3

So eq-3 shows that the elevation of BP is proportional to mole

fraction of solute so BP is colligative property.
In dilute solution X2 = m/(1000/M1)
So equation 3 can be rearranged as

ΔTb = k M1 m ---------Eq-4
1000
Or

ΔTb = Kb m ---------Eq-5

ΔT=
b
boiling point elevation
m = solution molality
Kb = molal elevation constant or Ebullioscopic constant = Increase in BP
of solvent caused by the addition of 1 mole of solute (non-volatile and
non electrolyte) in 1 Kg of volatile solvent.
 Examples
Q=1An aqueous solution of a drug gave a boiling point elevation (ΔTb)
of 0.103°C. The molal elevation constant for water is 0.515 deg
kg/mole. Calculate the solution concentration.
T − To = ΔTb = Kb m
m = 0.103°C / 0.515 deg kg/mole
= 0.2 mol/kg
Q=2 A 0.200 m aqueous solution of a drug gave a boiling point elevation of
0.103°C.
Calculate the approximate molal elevation constant for the solvent,
water.
Kb = ΔTb / m = 0.103°C / 0.200
= 0.515 deg kg/ mol

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 BP Elevation of non-volatile and electrolyte solute

• In case, when any non-volatile and electrolyte is dissolved in

the solvent, the lowering in the vapour pressure will be
abnormally high than that of the non- electrolyte.
• This is because, the electrolyte dissociate into ions in the
solution, so no. of the particle will increased and as a result,
lowering in vapour pressure will also high.
• There fore elevation in boiling point of non volatile electrolyte
is also greater than that in case of non-volatile non electrolyte.
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Questions !
3-Depression in freezing point
• Imagine the freezing process this way. When the temperature is
held at the freezing point of a pure solvent, freezing begins with
a few molecules clustering together to form a tiny amount of
solid. More molecules of the liquid move to the surface of the
solid, and the solid grows.

• Here the heat of fusion, is evolved; as long as this heat energy is

removed, solidification continues.

• If the heat is not removed, however, the opposing processes of

freezing and melting can come into equilibrium; at this point, the
number of molecules moving from solid to liquid is the same as
the number moving from liquid to solid in a given time
• The FP of solution is define as “ The temperature at which the
solid and liquid forms of the solvent co-exist in equilibrium at
fixed external pressure. (1 atmospheric pressure)”
• Equilibrium here means that the tendency for the solid to pass
in the liquid state is the same as tendency for the reverse
process to occur, b/c liquid and the solid have the same
escaping tendency.
• FP depression: When a non volatile solute is dissolved in a
pure solvent, then it will freeze at a lower temperature than the
temperature at which pure solvent freezes. And this difference
in freezing point b/w the pure solvent and solution is called the
FP depression.
Freezing Point Depression
Explanation:
• One way to explain is in term of VP, FP is the temperature at
which the vapour pressure of the substance in its liquid phase
is equal to its vapour pressure in its solid phase.
• As the vapour pressure of the solution is lower than that of
pure solvent so it is obvious that the liquid and frozen form of
solution cant be co exist in equilibrium (this is because at
equilibrium both states must have same vapour pressure).
• They can now co – exist at some lower temperature (new
freezing point), where the liquid and frozen form of solution
have the same vapour pressure.
• That’s why freezing point of the solution will be lowered upon
addition of solute.
• For dilute solution, the depression of freezing point is directly
proportional to molality (molal concentration) of the solution.
• Greater no. of particles= lower of V.P= More depression in
F.P
Explanation:
• Other way to explain is that the liquid layer next to the solid contains
solute molecules or ions, whereas the solid is pure solvent. If the
temperature is held at the normal freezing point of the pure solvent,
the number of molecules of the solid (pure solvent) entering the
liquid phase must therefore be greater than the number of solvent
molecules leaving the solution and depositing on the solid in a given
time.
• Why? Because the vapor pressure of a solution is lower than that of
the pure solvent. As solute molecules have replaced some solvent
molecules in the liquid at the liquid/solid interface
• Thus, to have the same number of solvent molecules moving in each
direction in a given time, the temperature must be lowered so that it
slow down movement from solid to liquid phase. That is the reason
that the freezing temperature of a solution must be less than that of
the pure liquid solvent
 Graphical Representation of Depression of the freezing point

Hence, freezing point

depression is also proportional
to the molal concentration of the
solution.

To − T = ΔTf = Kfm
where:
To = freezing point of the solvent
T = freezing point of the solution
ΔTf = freezing point depression
m = solution molality • Phase diagram showing the effect of
Kf = molal depression constant nonvolatile solute on freezing point and
(characteristic of the solvent) boiling point.
• Purple = solution
• Blue = pure solvent
 Examples on FP
Q1=What is the freezing point depression of a 1.3 m solution of sucrose
in water? When the cryoscopic constant at this concentration is about

ΔTf = Kfm = 2.1 x 1.3 = 2.73°C

Q2=What is the freezing point of a solution containing 3.42 g of

sucrose and 500 g of water?

The molecular weight of sucrose is 342. In this relatively dilute

solution, Kf is approximately equal to 1.86.

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 Applications

When salt is put on an icy road, the

salt mixes with a small amount of
liquid water to prevent melting ice
from re-freezing
 1. salting roads in winter

BP
FP
100oC
water 0oC (NFP)
(NBP)
water + a little salt –11oC 103oC
water + more salt –18oC 105oC

2. antifreeze (AF) /coolant

BP
FP
100oC
water 0oC (NFP)
(NBP)
water + a little AF –10oC 110oC
50% water + 50% AF –35oC 130oC
4- Osmotic Pressure
• Osmosis is the spontaneous movement of water across a semi-permeable membrane
from an area of low solute13
Chapter concentration to an area of high solute concentration
• Osmotic Pressure - The Pressure that must be applied to stop osmosis i.e. to prevent the
passage of the solvent through a semi-permeable membrane
Carry on reading from
Martin’s Physical
Pharmacy and
Pharmaceutical
Sciences, sixth edition
p 122 - 126.

In osmosis, there is net movement of solvent from the area of higher

solvent concentration (lower solute concentration) to the area of
lower solvent concentration (higher solute concentration).
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van't Hoff Equations for Osmotic Pressure

Osmotic pressure, π
– excess pressure which must be applied to a solution to prevent the
passage of solvent through the semi-permeable membrane.

– van’t Hoff equation relates osmotic pressure to solution concentration

Where
π is the osmotic pressure .
V is the volume of the solution in liters.
n is the number of moles of solute.
R is the gas constant, equal to 0.082 liter atm/mole
deg.
T is the absolute temperature.
 Examples
Q1=One gram of sucrose (MW = 342) is dissolved in 100ml of solution at
25°C.What is the osmotic pressure of the solution?

Q2=What is the osmotic pressure of 50 g dextrose in 1000 mL of water at

room temperate (25°C)?

1. n = (50 g dextrose)/(MW of 180) = 0.28 moles of dextrose

2. T = 273°C + 25°C = 298°C
3. V = Volume will be 1 L
4. Π = [(0.28)(0.082)(298)]/(1) = 6.84 atm

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Osmotic pressure of Electrolytes:
• The osmotic pressure of the electrolytes is greater than the
same molal concentration of non-electrolytes.
• The electrolytes in solution form dissociate into ions, so the #
of particles are increased, hence the osmotic pressure is also
increased. e.g.
• NaCl  Na+ + Cl-
• Deviations from reality in the above ideal examples of
colligative properties are explained by the use of the Van't
Hoff term, i.
 ∏V=inRT,
• This "i" term considers that electrolytes exert more pressure than
nonelectrolytes and is related to the number of ionic species
present. These deviations may be caused by ionic interaction,
degree of dissociation of weak electrolytes.
• It is evident that each molecule of NaCl is ionized to produce two
ions and if NaCl completely ionizes there will be twice as many
particles as would the case of non-ionized form. Thus the osmotic
pressure will be doubled.
 Osmosis and Blood Cells
(a)A cell placed in an isotonic solution. The net movement of water in and out
of the cell is zero because the concentration of solutes inside and outside the
cell is the same.
(b)In a hypertonic solution, the concentration of solutes outside the cell is
greater than that inside. There is a net flow of water out of the cell, causing the
cell to dehydrate, shrink, and perhaps die.
(c)In a hypotonic solution, the concentration of solutes outside of the cell is less
than that inside. There is a net flow of water into the cell, causing the cell to
swell and perhaps to burst.
• Nonelectrolytes, the solution will contain only molecules, and the
osmotic pressure will vary only with concentration of the solute.
• Electrolytes: solution will contain ions, and the osmotic pressure
of the solution will vary not only with the concentration but also
with the degree of dissociation of the solute.
• Isosmotic solutions: solutions that have the same osmotic
pressure
• Isotonic solution: a solution having the same osmotic pressure as
a
specific body fluid
• Hypotonic solution: a solution of lower osmotic pressure than
that of body fluids.
• Hypertonic solution: a solution of higher osmotic pressure than
that of
body fluids.
• Important for the pharmacist for preparation of ophthalmic,
nasal, parenteral and some rectal preparations. 43
 Choice of Colligative Properties
1. The boiling point method can be used only when the solute is
nonvolatile and when the substance is not decomposed at boiling
temperatures
2. The freezing point method is satisfactory for solutions containing
volatile solutes, such as alcohol, because the freezing point of a
solution depends on the vapor pressure of the solvent alone.
3. Osmotic pressure measurements used when it is sometimes
inconvenient to use freezing point or boiling point methods because
it carried out at definite temperatures
4. vapor pressure techniques are the methods of choice, except for high
polymers, in which instance the osmotic pressure method is used.
5. The colligative properties can be used to calculate the Mw
of nonelectrolytes present as solutes.
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 Practical Applications of CP
1-One of the most important pharmaceutical applications of colligative
properties is in the preparation of isotonic intravenous and lachrymal solutions.

2-Other applications of the Colligative properties are found in experimental

physiology.
One such application is in the immersion of tissues in salt solutions,
which are isotonic with the fluids of the tissue, in order to prevent changes or
injuries that may arise from osmosis.

3-The Colligative properties of solutions also may be used in determining the

molecular weight of solutes,
In the case of electrolytes, the extent of ionization.
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Questions !